KR101532299B1 - New electron transporting compounds and organic electroluminescent device comprising the same - Google Patents

Abstract

상기 전자수송 화합물은 유기전기발광소자의 발광효율 및 소자 수명을 향상시킬 수 있다.
The present invention provides an electron transport compound represented by the following formula (1) and an organic electroluminescent device comprising the same:
[ Chemical Formula 1 ]

The electron transport compound can improve the luminous efficiency and lifetime of the organic electroluminescent device.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a novel electron transport compound and an organic electroluminescent device including the same. BACKGROUND ART < RTI ID = 0.0 >

The present invention relates to a novel electron transport compound and an organic electroluminescent device comprising the same.

An organic electronic device is an electronic device using an organic semiconductor material, and requires holes and / or electrons to flow between the electrode and the organic semiconductor material. The organic electronic device can be broadly classified into two types according to the operating principle as described below. First, an exciton is formed in an organic material layer by a photon introduced into an element from an external light source. The exciton is separated into an electron and a hole, and the electrons and holes are transferred to different electrodes to be used as a current source Type electronic device. The second type is an electronic device that injects holes and / or electrons into an organic semiconductor material layer that interfaces with the electrode by applying a voltage or current to two or more electrodes, and operates by injected electrons and holes.

Examples of the organic electronic device include an organic light emitting device, an organic solar cell, an organic photoconductor (OPC) drum, and an organic transistor. All of them include an electron / hole injecting material, an electron / hole extracting material, A transport material or a luminescent material. Hereinafter, the organic light emitting device will be described in detail, but in the organic electronic devices, the electron / hole injecting material, the electron / hole extracting material, the electron / hole transporting material, or the light emitting material all have a similar principle.

In general, organic light emission phenomenon refers to a phenomenon in which an organic material is used to convert electric energy into light energy.

An organic light emitting device using an organic light emitting phenomenon usually has a structure including an anode and a cathode and an organic layer between them. Here, in order to increase the efficiency and stability of the organic light emitting device, the organic material layer may have a multi-layer structure composed of different materials and may include a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer. When a voltage is applied between two electrodes in the structure of the organic light emitting device, holes are injected into the anode, electrons are injected into the organic layer, electrons are injected into the organic layer, excitons are formed when injected holes and electrons meet, When it falls to a state, it becomes a light. Such an organic light emitting device is known to have characteristics such as self-emission, high luminance, high efficiency, low driving voltage, wide viewing angle, high contrast, and high speed response.

A material used as an organic material layer in an organic light emitting device can be classified into a light emitting material and a charge transporting material such as a hole injecting material, a hole transporting material, an electron transporting material, and an electron injecting material depending on functions. The light emitting material can be classified into blue, green and red light emitting materials and yellow and orange light emitting materials necessary for realizing better natural color depending on the luminescent color. Further, in order to increase the color purity and increase the luminous efficiency through energy transfer, a host / dopant system can be used as a light emitting material. The principle is that a small amount of dopant having a smaller energy band gap and a higher luminous efficiency than a host mainly constituting the light emitting layer is mixed with the light emitting layer in a small amount, and the excitons generated in the host are transported to the dopant to emit highly efficient light. At this time, since the wavelength of the host is shifted to the wavelength band of the dopant, the desired wavelength light can be obtained depending on the type of the dopant used.

In order to sufficiently exhibit the excellent characteristics of the organic light emitting device, a material constituting the organic material layer in the device such as a hole injecting material, a hole transporting material, a light emitting material, an electron transporting material, and an electron injecting material is supported by a stable and efficient material Should be preceded.

Among them, organometallic complexes having a relatively high stability to electrons and an electron transfer rate as organic monomolecular materials are preferable as electron transporting materials. Among them, Alq3 having excellent stability and high electron affinity has been reported to be the most excellent, but when it is used in a blue light emitting device, there is a problem that the color purity drops due to exciton diffusion. Flavon derivatives of sanyo or germanium and silicon clopetadiene derivatives of Chisso are known (Japanese Patent Laid-Open Publication No. 1998-017860, Japanese Laid-Open Patent Publication No. 1999-087067 ).

As the organic monomolecular substance, a PBD (2-biphenyl-4-yl-5- (4-t-butylphenyl) -1,3,4-oxadiazole) derivative bonded to a Spiro compound and a hole blocking ability (2,2 ', 2 "- (benzene-1,3,5-triyl) -tris (1-phenyl-1H-benzimidazole) which has both excellent electron transporting ability , 1998, 1136 & Tao et al, Appl. Phys. Lett., 77, 2000, 1575), and benzoimidazole derivatives disclosed in LG Chem are widely known for their excellent durability.

Organic light emitting devices using the organic single molecular material as an electron transporting layer have short lifetime, low storage durability and low reliability. These problems are caused by physical or chemical changes of organic materials, photochemical or electrochemical changes of organic materials, oxidation and peeling of the cathodes, and durability.

Therefore, organic light emitting devices using a method of obtaining arbitrary luminescent color by changing the structure of an organic monomolecular material used in an organic luminescent device or obtaining various high efficiencies by a host dopant system have been proposed, Characteristics, life span and durability.

For example, Korean Patent Publication No. 2003-0067773 discloses a compound having a benzoimidazole and an anthracene skeleton.

However, there is a continuing need for the development of new materials that can provide even higher luminous brightness, luminous efficiency, lifetime, and the like to organic electroluminescent devices than these compounds.

It is an object of the present invention to provide a novel electron transport compound capable of lowering a driving voltage when applied to an organic electroluminescent device and improving luminescence efficiency, luminance, thermal stability and device life.

It is another object of the present invention to provide an organic electroluminescence device employing the above compound.

The present invention provides an electron transport compound represented by the following Formula 1:

[Chemical Formula 1]

In this formula,

X is a carbon atom or a nitrogen atom;

R 1, R 2, R 3 and R 4 are each independently a hydrogen atom, a straight chain alkyl of C 1 to C 10, a branched chain alkyl of C 3 to C 10, a straight chain alkoxy of C 1 to C 10, a branched chain alkoxy of C 3 to C 10, ₃ , Si (CH ₃ ) ₃ or Si (C ₆ H ₅ ) ₃ ,

Small wish chair, C1 ~ C10 straight chain alkyl, branched alkyl, halogen, nitrile of _{C3 ~ C10, CF 3, Si} (CH 3) 3, Si (C 6 H 5) 3, phenyl, biphenyl and naphthyl groups An aryl group having 6 to 30 carbon atoms or a heteroaryl group having 5 to 60 carbon atoms, which is substituted or unsubstituted with at least one substituent selected from the group consisting of

R5 and R6 are the same and, C1 ~ C10 straight chain alkyl, a C3 ~ C10 branched chain alkyl, straight chain alkoxy, branched chain alkoxy, halogen, nitrile of C3 ~ C10 of C1 ~ C10 each _{other, CF 3, Si (CH 3} ) ₃ or Si (C ₆ H ₅ ) ₃ ,

로 이루어진 군으로부터 선택되는 하나 이상의 치환기로 치환 또는 비치환된 탄소수 6~30의 아릴기 또는 탄소수 5~60의 헤테로아릴기이며, 상기 Ar1 및 Ar2는 각각 독립적으로 중소소원자, C1~C10의 직쇄 알킬, C3~C10의 분지쇄 알킬, C1~C10의 직쇄 알콕시, C3~C10의 분지쇄 알콕시, 할로겐, 니트릴, CF₃,Si(CH₃)₃및 Si(C₆H₅)₃로 이루어진 군으로부터 선택되는 하나 이상의 치환기로 치환 또는 비치환된 탄소수 6~30의 아릴기 또는 탄소수 5~60의 헤테로아릴기이며;Small wish Here, C1 ~ C10 straight chain alkyl, a C3 ~ C10 branched chain alkyl, straight chain alkoxy, branched chain alkoxy, halogen, nitrile of C3 ~ C10 of _{C1 ~ C10, CF 3, Si} (CH 3) 3, Si ( C ₆ H ₅ ) ₃ , phenyl, biphenyl, naphthyl, carbazole, and

, Ar1 and Ar2 each independently represent a group selected from the group consisting of a small and medium-sized ligand, a linear or branched C 1 to C 10 linear or branched alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms or a substituted or unsubstituted heteroaryl group having 5 to 60 carbon atoms, alkyl, the group consisting of C3 ~ C10 branched chain alkyl, straight chain alkoxy, branched chain alkoxy, halogen, nitrile of C3 ~ C10 of _{C1 ~ C10, CF 3, Si} (CH 3) 3 and Si (C ₆ H _{5) 3} An aryl group having 6 to 30 carbon atoms or a heteroaryl group having 5 to 60 carbon atoms which is substituted or unsubstituted with at least one substituent selected from

R7 and R8 are each independently selected from the group consisting of a hydrogen atom, C1-C10 straight chain alkyl, C3-C10 branched alkyl, C1-C10 cycloalkyl, C1-C10 linear alkoxy, C3- _{nitrile, CF 3, Si (CH 3} ) 3 or Si (C ₆ H _{5) 3,} or,

기일 수 있으며;C 1 -C 10 straight chain alkoxy, halogen, nitrile, nitro, CF ₃ , Si (CH ₃ ) ₃ , C 1 -C 10 linear or branched alkyl, (C ₆ H ₅ ) ₃ , phenyl, naphthyl, phenanthrenyl, fluorenyl, tetrahydropyrrole, pyrrole, thienyl, thienyl, Thiophene, pyrazole, oxazolyl, triazole, pyridinyl, pyrimidinyl, triazinyl, imidazole, benzoxazole, benzothiazole, carbazole, dibenzofuran, dibenzothiophene, benzimidazole, Quinolinyl, indole, pyrenyl or

Lt; / RTI >

,

,

,

,

또는

을 형성할 수 있으며, 상기 R9, R10, R11 및 R12는, 각각 독립적으로, 수소원자, C1~C10의 직쇄 알킬, C3~C10의 분지쇄 알킬, C1~C10의 직쇄 알콕시, C3~C10의 분지쇄 알콕시, 할로겐, 니트릴, 아세틸레닐, 페녹시, 니트로, CF₃,페녹시, Si(CH₃)₃또는Si(C₆H₅)₃이거나,R7 and R8 are bonded to, a small wish chair, C1 ~ C10 straight chain alkyl, branched alkyl, halogen, nitrile of _{C3 ~ C10, CF 3, Si} (CH 3) 3, Si (C 6 H 5) 3, phenyl , A biphenyl and a naphthyl group, or a substituted or unsubstituted C1-C4 alkylene, biphenyl, naphthyl, phenanthrenyl, fluorenyl, benzoxazole, benzothiazole, Carbazole, dibenzofuran, dibenzothiophene, benzimidazole, quinoline, indole, pyrenyl,

,

,

,

,

or

Each of R9, R10, R11 and R12 is independently selected from the group consisting of a hydrogen atom, a C1 to C10 linear alkyl, a C3 to C10 branched alkyl, a C1 to C10 linear alkoxy, a C3 to C10 branch chain alkoxy, halogen, nitrile, acetyl alkylenyl, phenoxy, nitro, CF _3, phenoxy, Si (CH _{3) 3} or Si (C ₆ H _{5) 3,} or,

일 수 있으며, 상기에서 R9 및 R10은 결합하여 C1~C4의 알킬렌을 형성할 수 있으며, R10 및 R11은 결합하여

,

,

,

또는

를 형성할 수 있으며, R11 및 R12는 결합하여 C1~C4의 알킬렌을 형성할 수 있다.Small wish chair, C1 ~ C10 straight chain alkyl, branched alkyl, halogen, nitrile of _{C3 ~ C10, CF 3, Si} (CH 3) 3, Si (C 6 H 5) 3, phenyl, biphenyl and naphthyl groups A substituted or unsubstituted heterocyclic group selected from the group consisting of phenyl, naphthyl, phenanthrenyl, fluorenyl, pyridinyl, pyrimidinyl, triazinyl, imidazole, benzoxazole, benzothiazole, carbazole , Dibenzofuran, dibenzothiophene, benzimidazole, quinolinyl, indole, pyrenyl, or

Wherein R9 and R10 may combine to form a C1-C4 alkylene, and R10 and R11 may be combined to form a

,

,

,

or

And R11 and R12 may combine to form a C1-C4 alkylene.

Further, according to the present invention,

An organic electroluminescent device in which an organic thin film layer composed of one layer or a plurality of layers including at least a light emitting layer is sandwiched between a cathode and an anode,

The organic thin film layer includes an electron transporting layer, and the electron transporting layer contains the electron transporting compound alone or in combination of two or more.

The electron transport compound according to the present invention lowers the driving voltage when applied to an organic light emitting device and improves luminous efficiency, luminance, thermal stability, and device lifetime.

The organic electroluminescent device manufactured using the electron transport compound of the present invention has high efficiency and long life characteristics.

The present invention relates to an electron transport compound represented by the following formula

[Chemical Formula 1]

In this formula,

X is a carbon atom or a nitrogen atom;

R 1, R 2, R 3 and R 4 are each independently a hydrogen atom, a straight chain alkyl of C 1 to C 10, a branched chain alkyl of C 3 to C 10, a straight chain alkoxy of C 1 to C 10, a branched chain alkoxy of C 3 to C 10, ₃ , Si (CH ₃ ) ₃ or Si (C ₆ H ₅ ) ₃ ,

Small wish chair, C1 ~ C10 straight chain alkyl, branched alkyl, halogen, nitrile of _{C3 ~ C10, CF 3, Si} (CH 3) 3, Si (C 6 H 5) 3, phenyl, biphenyl and naphthyl groups An aryl group having 6 to 30 carbon atoms or a heteroaryl group having 5 to 60 carbon atoms, which is substituted or unsubstituted with at least one substituent selected from the group consisting of

R5 and R6 are the same and, C1 ~ C10 straight chain alkyl, a C3 ~ C10 branched chain alkyl, straight chain alkoxy, branched chain alkoxy, halogen, nitrile of C3 ~ C10 of C1 ~ C10 each _{other, CF 3, Si (CH 3} ) ₃ or Si (C ₆ H ₅ ) ₃ ,

로 이루어진 군으로부터 선택되는 하나 이상의 치환기로 치환 또는 비치환된 탄소수 6~30의 아릴기 또는 탄소수 5~60의 헤테로아릴기이며, 상기 Ar1 및 Ar2는 각각 독립적으로 중소소원자, C1~C10의 직쇄 알킬, C3~C10의 분지쇄 알킬, C1~C10의 직쇄 알콕시, C3~C10의 분지쇄 알콕시, 할로겐, 니트릴, CF₃,Si(CH₃)₃및 Si(C₆H₅)₃로 이루어진 군으로부터 선택되는 하나 이상의 치환기로 치환 또는 비치환된 탄소수 6~30의 아릴기 또는 탄소수 5~60의 헤테로아릴기이며;Small wish Here, C1 ~ C10 straight chain alkyl, a C3 ~ C10 branched chain alkyl, straight chain alkoxy, branched chain alkoxy, halogen, nitrile of C3 ~ C10 of _{C1 ~ C10, CF 3, Si} (CH 3) 3, Si ( C ₆ H ₅ ) ₃ , phenyl, biphenyl, naphthyl, carbazole, and

, Ar1 and Ar2 each independently represent a group selected from the group consisting of a small and medium-sized ligand, a linear or branched C 1 to C 10 linear or branched alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms or a substituted or unsubstituted heteroaryl group having 5 to 60 carbon atoms, alkyl, the group consisting of C3 ~ C10 branched chain alkyl, straight chain alkoxy, branched chain alkoxy, halogen, nitrile of C3 ~ C10 of _{C1 ~ C10, CF 3, Si} (CH 3) 3 and Si (C ₆ H _{5) 3} An aryl group having 6 to 30 carbon atoms or a heteroaryl group having 5 to 60 carbon atoms which is substituted or unsubstituted with at least one substituent selected from

R7 and R8 are each independently selected from the group consisting of a hydrogen atom, C1-C10 straight chain alkyl, C3-C10 branched alkyl, C1-C10 cycloalkyl, C1-C10 linear alkoxy, C3- _{nitrile, CF 3, Si (CH 3} ) 3 or Si (C ₆ H _{5) 3,} or,

기일 수 있으며;C 1 -C 10 straight chain alkoxy, halogen, nitrile, nitro, CF ₃ , Si (CH ₃ ) ₃ , C 1 -C 10 linear or branched alkyl, (C ₆ H ₅ ) ₃ , phenyl, naphthyl, phenanthrenyl, fluorenyl, tetrahydropyrrole, pyrrole, thienyl, thienyl, Thiophene, pyrazole, oxazolyl, triazole, pyridinyl, pyrimidinyl, triazinyl, imidazole, benzoxazole, benzothiazole, carbazole, dibenzofuran, dibenzothiophene, benzimidazole, Quinolinyl, indole, pyrenyl or

Lt; / RTI >

,

,

,

,

또는

을 형성할 수 있으며, 상기 R9, R10, R11 및 R12는, 각각 독립적으로, 수소원자, C1~C10의 직쇄 알킬, C3~C10의 분지쇄 알킬, C1~C10의 직쇄 알콕시, C3~C10의 분지쇄 알콕시, 할로겐, 니트릴, 아세틸레닐, 페녹시, 니트로, CF₃,페녹시, Si(CH₃)₃또는Si(C₆H₅)₃이거나,R7 and R8 are bonded to, a small wish chair, C1 ~ C10 straight chain alkyl, branched alkyl, halogen, nitrile of _{C3 ~ C10, CF 3, Si} (CH 3) 3, Si (C 6 H 5) 3, phenyl , A biphenyl and a naphthyl group, or a substituted or unsubstituted C1-C4 alkylene, biphenyl, naphthyl, phenanthrenyl, fluorenyl, benzoxazole, benzothiazole, Carbazole, dibenzofuran, dibenzothiophene, benzimidazole, quinoline, indole, pyrenyl,

,

,

,

,

or

Each of R9, R10, R11 and R12 is independently selected from the group consisting of a hydrogen atom, a C1 to C10 linear alkyl, a C3 to C10 branched alkyl, a C1 to C10 linear alkoxy, a C3 to C10 branch chain alkoxy, halogen, nitrile, acetyl alkylenyl, phenoxy, nitro, CF _3, phenoxy, Si (CH _{3) 3} or Si (C ₆ H _{5) 3,} or,

일 수 있으며, 상기에서 R9 및 R10은 결합하여 C1~C4의 알킬렌을 형성할 수 있으며, R10 및 R11은 결합하여

,

,

,

또는

를 형성할 수 있으며, R11 및 R12는 결합하여 C1~C4의 알킬렌을 형성할 수 있다.Small wish chair, C1 ~ C10 straight chain alkyl, branched alkyl, halogen, nitrile of _{C3 ~ C10, CF 3, Si} (CH 3) 3, Si (C 6 H 5) 3, phenyl, biphenyl and naphthyl groups A substituted or unsubstituted heterocyclic group selected from the group consisting of phenyl, naphthyl, phenanthrenyl, fluorenyl, pyridinyl, pyrimidinyl, triazinyl, imidazole, benzoxazole, benzothiazole, carbazole , Dibenzofuran, dibenzothiophene, benzimidazole, quinolinyl, indole, pyrenyl, or

Wherein R9 and R10 may combine to form a C1-C4 alkylene, and R10 and R11 may be combined to form a

,

,

,

or

And R11 and R12 may combine to form a C1-C4 alkylene.

In the above formula (1), an aryl group having 6 to 30 carbon atoms or a heteroaryl group having 5 to 60 carbon atoms is preferably a phenyl, naphthyl, phenanthrenyl, fluorenyl, pyridinyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazinyl, Imidazole, triazole, benzoxazole, benzothiazole, carbazole, dibenzofuran, dibenzothiophene, benzimidazole, quinolinyl, indole or pyrenyl group.

In Formula 1, more preferably,

X is a carbon atom or a nitrogen atom;

R 1, R 2, R 3 and R 4 are each independently a hydrogen atom, a phenyl or biphenyl group;

R5 and R6 are the same, and a C1 ~ C10 straight chain alkyl, C3 ~ C10 straight chain of branched chain alkyl, C1 ~ C10 alkoxy, or a C3 ~ C10 branched alkoxy, halogen, nitrile, or CF ₃ each other,

로 이루어진 군으로부터 선택되는 하나 이상의 치환기로 치환 또는 비치환된 페닐, 나프틸 또는 플루오레닐기이며, 상기 Ar1 및 Ar2는 각각 독립적으로 C1~C10의 직쇄 알킬, C3~C10의 분지쇄 알킬기로 치환 또는 비치환된 페닐, 바이페닐, 플루오레닐 또는 피리디닐기이며;C1 ~ C10 straight chain alkyl, C3 ~ C10 branched chain alkyl, straight chain alkoxy, branched chain alkoxy, halogen, nitrile of C3 ~ C10 ~ C10 of the C1, CF _3, phenyl, biphenyl, carbazole and

Naphthyl or fluorenyl group which is unsubstituted or substituted with one or more substituents selected from the group consisting of C1-C10 straight-chain alkyl, substituted or unsubstituted C3-C10 branched alkyl group, Unsubstituted phenyl, biphenyl, fluorenyl or pyridinyl group;

R7 and R8 are, each independently, a hydrogen atom, C1 ~ C10 straight chain alkyl, a C3 ~ C10 branched alkyl, C1 ~ C10 cycloalkyl, halogen, or nitrile, or CF _3;

기일 수 있으며;C1 ~ C10 straight chain alkyl, unsubstituted or substituted with one or more substituents selected from the group consisting of C3 ~ C10 branched alkoxy, halogen, nitrile, nitro and CF _3, phenyl, tetrahydro-pyrrole, thiophenyl,

Lt; / RTI >

,

,

,

,

또는

을 형성할 수 있으며, 상기 R9, R10, R11 및 R12는 각각 독립적으로, 수소원자, C1~C10의 직쇄 알킬, C3~C10의 분지쇄 알킬, C1~C10의 직쇄 알콕시, C3~C10의 분지쇄 알콕시, 할로겐, 니트릴, 아세틸레닐, 니트로, CF₃,Si(CH₃)₃,페닐, 피리디닐, 페녹시, 퀴놀리닐 또는

일 수 있으며, 상기에서 R9 및 R10은 결합하여 C1~C4의 알킬렌을 형성할 수 있으며, R10 및 R11은 결합하여

,

,

,

또는

를 형성할 수 있으며, R11 및 R12는 결합하여 C1~C4의 알킬렌을 형성할 수 있다. R7 and R8 are bonded to form a C1-C4 alkylene, a biphenyl, a naphthyl, a phenanthrenyl, a phenanthrenyl group, a phenanthrenyl group,

,

,

,

,

or

Wherein R9, R10, R11 and R12 are each independently selected from the group consisting of a hydrogen atom, C1 to C10 linear alkyl, C3 to C10 branched alkyl, C1 to C10 linear alkoxy, C3 to C10 branched alkoxy, halogen, nitrile, acetyl alkylenyl, _{nitro, CF 3, Si (CH 3} ) 3, phenyl, pyridinyl, phenoxy, quinolinyl or

Wherein R9 and R10 may combine to form a C1-C4 alkylene, and R10 and R11 may be combined to form a

,

,

,

or

And R11 and R12 may combine to form a C1-C4 alkylene.

The electron transport compound of the present invention can be usefully used in organic electroluminescent devices.

The electron transport compound of the present invention may have the chemical structure shown in the following [first group (s)].

[First group (group)]

The present invention also relates to

An organic electroluminescent device in which an organic thin film layer composed of one layer or a plurality of layers including at least a light emitting layer is sandwiched between a cathode and an anode,

The organic thin film layer includes an electron transporting layer, and the electron transporting layer contains the electron transporting compound of the present invention singly or in combination of two or more.

The organic electroluminescent device

An anode, a hole injecting layer, a hole transporting layer, a light emitting layer, an electron transporting layer, an electron injecting layer, and a cathode stacked in this order.

Hereinafter, the organic electroluminescent device of the present invention will be described by way of example. However, the following examples do not limit the organic electroluminescent device of the present invention.

The organic electroluminescent device of the present invention may have a structure in which a cathode (a hole injection electrode), a hole injection layer (HIL) and / or a hole transport layer (HTL), a light emitting layer (EML) Preferably, an electron blocking layer (EBL) may be additionally provided between the anode and the light emitting layer, and an electron transport layer (ETL), an electron injection layer (EIL) or a hole blocking layer (HBL) have.

In the method of manufacturing an organic electroluminescence device according to the present invention, a cathode material is coated on the surface of a substrate by a conventional method to form a cathode. At this time, the substrate to be used is preferably a glass substrate or a transparent plastic substrate having excellent transparency, surface smoothness, ease of handling, and waterproofness. As the material for the positive electrode, indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO2), zinc oxide (ZnO) and the like which are transparent and excellent in conductivity may be used.

Next, a hole injection layer (HIL) material is formed on the surface of the anode by vacuum thermal deposition or spin coating using a conventional method. Examples of such hole injecting materials include copper phthalocyanine (CuPc), 4,4 ', 4 "-tris (3-methylphenylamino) triphenylamine (m-MTDATA), 4,4' ), 4,4 ', 4 "-tri (N-carbazolyl) triphenylamine (TCTA), 4,4', 4" -tris (2-naphthyl) -N-phenylamino) -triphenylamine (2-TNATA) or IDE406 available from Idemitsu.

A hole transport layer (HTL) material is vacuum-deposited or spin coated on the surface of the hole injection layer by a conventional method to form a hole transport layer. As the hole transporting material, bis (N- (1-naphthyl-n-phenyl)) benzidine (? -NPD), N, N'- -Benzidine (NPB) or N, N'-diphenyl-N, N'-bis (3-methylphenyl) -1,1'-diphenyl-4,4'-diamine (TPD).

A light emitting layer (EML) material is formed on the surface of the hole transport layer by vacuum thermal deposition or spin coating using a conventional method. Among the light emitting layer materials used, tris (8-hydroxyquinolinolato) aluminum (Alq3) is used as a sole luminescent material or luminescent host material, Balq (8-hydroxyquinoline beryllium salt) DPVBi (4,4'-bis (2,2-diphenyletheryl) -1,1'-biphenyl) series, Spiro material, Spiro- DPVBi (spiro- Biphenyl), LiPBO (2- (2-benzoxazolyl) -phenol lithium salt), bis (diphenylvinyl) benzene, aluminum-quinoline metal complex , Metal complexes of imidazole, thiazole and oxazole, and the like.

Among the light emitting layer materials, IDE102 and IDE105 available from Idemitsu as phosphorescent dopants and tris (2-phenylpyridine) iridium (III) (Ir (ppy ) 3), iridium (III) bis [(4,6-difluorophenyl) pyridinate-N, C-2 '] picolinate (FIrpic) (Chihaya Adachi et al., Appl. Phys Platy (II) octaethylporphyrin (PtOEP), TBE002 (Cobion), etc. may be used.

An electron transport layer (ETL) material is formed on the surface of the light emitting layer by vacuum thermal deposition or spin coating using a conventional method. In this case, the electron transporting compound of the present invention can be preferably used for the electron transporting material to be used. In addition, tris (8-hydroxyquinolinolato) aluminum (Alq3) can be used.

Alternatively, by further forming a hole blocking layer (HBL) between the light emitting layer and the electron transporting layer and using a phosphorescent dopant together with the light emitting layer, it is possible to prevent the phenomenon that the triplet excitons or holes are diffused into the electron transporting layer.

The hole blocking layer can be formed by vacuum thermal deposition and spin coating using a hole blocking layer material in a conventional manner. In the case of the hole blocking layer material, there is no particular limitation, but (8-hydroxyquinolinolato Lithium biphenoxide (BAlq), bathocuproine (BCP), LiF, etc. may be used as the lithium salt (Li), bis (8-hydroxy-2-methylquinolinonato)

An electron injection layer (EIL) material is formed on the surface of the electron transport layer by vacuum thermal deposition or spin coating using a conventional method. At this time, the electron injecting material to be used is not particularly limited, and preferably, materials such as LiF, Liq, Li2O, BaO, NaCl, and CsF can be used.

Finally, a negative electrode is formed on the surface of the electron injecting layer by vacuum thermal deposition using a conventional method.

At this time, as the negative electrode material to be used, lithium, aluminum, aluminum-lithium, calcium, magnesium, (Mg-Ag) or the like may be used. In the case of a top emission organic electroluminescent device, indium tin oxide (ITO) or indium zinc oxide (IZO) may be used to form a transparent cathode capable of transmitting light.

The organic electroluminescent device according to the present invention may be manufactured in the order as described above, that is, in the order of anode / hole injection layer / hole transport layer / light emitting layer / hole blocking layer / electron transport layer / electron injection layer / cathode, Electron injection layer / electron transporting layer / hole blocking layer / light emitting layer / hole transporting layer / hole injecting layer / anode.

Hereinafter, a method of synthesizing the compounds of the present invention will be described with reference to representative examples. However, the method of synthesizing the compounds of the present invention is not limited to the following exemplified methods, and the compounds of the present invention can be produced by the methods exemplified below and by methods known in the art.

Synthesis Example 1: Synthesis of Compound 14

[Reaction Scheme 1]

Preparation of intermediate compound [14-1]

In a 1 L reaction flask, 63.0 g (0.3 mol) of 1,10-phenanthroline-5,6-dione and 63.0 g (0.3 mol) of 1,3-diphenylacetone were stirred in 750 mL of methanol in a nitrogen atmosphere. 31.8 g (0.15 mol) of potassium phosphate is slowly added at room temperature. After stirring at room temperature for 2 hours, the resulting solid is filtered. The dark gray solid was vacuum dried to give 43 g (37%).

Preparation of compound [14]

22.0 g (57.23 mmol) of the intermediate compound [14-1] and 6.28 mL (57.23 mmol) of phenylacetylene were stirred in a reaction flask with 200 mL of butyl ether. The mixture was heated to reflux and stirred at 160 DEG C for 2 hours. Cool to room temperature and filter the resulting solid. The brown solid was recrystallized from dichloromethane and ethyl acetate to give 16.0 g (61%) of the target compound [14] as a white solid.

Synthesis Example 2: Synthesis of Compound 83

[Reaction Scheme 2]

Preparation of intermediate compound [83-1]

In a 1 L reaction flask, 20 g (52.03 mmol) of the intermediate compound [14-1] and 10.7 g (78.05 mmol) of anthranilic acid were stirred at room temperature with 500 mL of dichloroethane. 20.8 mL (0.156 mol) of isoamyl nitrite is slowly dropped at room temperature. The reaction temperature is slowly raised and stirred at reflux for 3 hours. When the reaction is completed, the reaction mixture is cooled to room temperature, and 1% sodium hydroxide solution and ethanol are added thereto. The reaction mixture was extracted with dichloromethane, the organic layer was separated, dried over anhydrous magnesium sulfate, and filtered. The filtrate was concentrated under reduced pressure and recrystallized from dichloromethane and acetone to obtain 15 g (62%) of intermediate compound [83-1] as a yellow solid.

Preparation of compound [83]

To the reaction flask, 15.0 g (32.57 mmol) of the intermediate compound [83-1] was stirred with 100 mL of nitrobenzene, and the mixture was subjected to pressure reaction at 200 ° C. After 12 hours of reaction, cool to room temperature. Methanol is added to the reaction solution to solidify it. The resulting solid is filtered and washed with methanol. The solid was recrystallized from dichloromethane and methanol to give 10.5 g (75%) of the target compound [83].

Compounds 1 to 152 were prepared in the same manner as in Synthesis Examples 1 and 2, and the results are shown in [Table 2].

[Second group (group)]

Hereinafter, the present invention will be described in more detail by way of examples. However, the following examples are intended to further illustrate the present invention, and the scope of the present invention is not limited by the following examples. The following examples can be appropriately modified and changed by those skilled in the art within the scope of the present invention.

Comparative Example 1

A compound represented by the following formula (a) is used as a fluorescent green host and a compound (b) represented by the following formula (b) is used as a fluorescent green dopant, and 2-TNATA (4,4 ' 2-yl) -N-phenylamino) -triphenylamine as a hole injecting material and α-NPD (naphthylene-1-yl) -N, N'-diphenylbenzidine as a hole transporting material ITO / 2-TNATA (80 nm) /? -NPD (30 nm) /? - NPD was used as a hole transporting material, and Alq3 was used as an electron transporting material and LiF was used as an electron injecting material. Compound a + compound b (30 nm) / Alq3 (30 nm) / LiF (0.5 nm) / Al (60 nm).

The anode was prepared by cutting a 15 Ω / cm ² (1000 Å) ITO glass substrate from Corning into a 50 mm × 50 mm × 0.7 mm size, ultrasonically cleaning it in acetone, isopropyl alcohol and pure water for 15 minutes each, Ozone cleaning was used. 2-TANATA was vacuum-deposited on the substrate to form a hole injection layer having a thickness of 80 nm. On top of the hole injection layer,? -NPD was vacuum deposited to form a hole transport layer having a thickness of 30 nm. Compound (a) represented by Formula (a) and compound (b) represented by Formula (b) (3% doped) were vacuum deposited on the hole transport layer to form a 30 nm thick light emitting layer. Then, an Alq3 compound was vacuum deposited on the light emitting layer to a thickness of 30 nm to form an electron transporting layer. LiF 0.5 nm (electron injection layer) and Al 60 nm (cathode) were sequentially vacuum-deposited on the electron transporting layer to form an organic light emitting device as shown in the third table group (3). This is referred to as Comparative Sample 1.

Examples 1-22.

ITO / 2-TNATA (80 nm) / electron transporting compound was prepared in the same manner as in Comparative Example 1, except that the compounds described in Synthesis Example were used as the electron transporting compound in place of the compound c (Alq3) an organic light emitting device having a structure of? -NPD (30 nm) / compound a + compound b (30 nm) / one of the electron transport compounds described in the above Synthesis Examples / LiF (0.5 nm) / Al (60 nm) was prepared. These are referred to as Samples 1 to 22, respectively.

Evaluation Example 1: Evaluation of luminescence characteristics of Comparative Sample 1 and Samples 1 to 22

Comparative Example 1 and Samples 1 to 22 were evaluated for light emission luminance, luminous efficiency and emission peak using Keithley SMU 235 and PR650, respectively, and the results are shown in the following [third group (group)]. The samples showed green emission peak values in the range of 514 to 524 nm.

[Group 3]

Samples 1 to 22 exhibited improved luminescent properties as compared to Comparative Sample 1, as shown in [third set of group (s)].

Claims (6)

An electron transport compound represented by the following Formula 1:
[Chemical Formula 1]

In this formula,
X is a carbon atom or a nitrogen atom;
R 1, R 2, R 3 and R 4 are each independently a hydrogen atom, a straight chain alkyl of C 1 to C 10, a branched chain alkyl of C 3 to C 10, a straight chain alkoxy of C 1 to C 10, a branched chain alkoxy of C 3 to C 10, ₃ , Si (CH ₃ ) ₃ or Si (C ₆ H ₅ ) ₃ ,
Small wish chair, C1 ~ C10 straight chain alkyl, branched alkyl, halogen, nitrile of _{C3 ~ C10, CF 3, Si} (CH 3) 3, Si (C 6 H 5) 3, phenyl, biphenyl and naphthyl groups An aryl group having 6 to 30 carbon atoms or a heteroaryl group having 5 to 60 carbon atoms, which is substituted or unsubstituted with at least one substituent selected from the group consisting of
R5 and R6 are the same and, C1 ~ C10 straight chain alkyl, a C3 ~ C10 branched chain alkyl, straight chain alkoxy, branched chain alkoxy, halogen, nitrile of C3 ~ C10 of C1 ~ C10 each _{other, CF 3, Si (CH 3} ) ₃ or Si (C ₆ H ₅ ) ₃ ,
Small wish Here, C1 ~ C10 straight chain alkyl, a C3 ~ C10 branched chain alkyl, straight chain alkoxy, branched chain alkoxy, halogen, nitrile of C3 ~ C10 of _{C1 ~ C10, CF 3, Si} (CH 3) 3, Si ( C ₆ H ₅ ) ₃ , phenyl, biphenyl, naphthyl, carbazole, and

, Ar1 and Ar2 each independently represent a group selected from the group consisting of a small and medium-sized ligand, a linear or branched C 1 to C 10 linear or branched alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms or a substituted or unsubstituted heteroaryl group having 5 to 60 carbon atoms, alkyl, the group consisting of C3 ~ C10 branched chain alkyl, straight chain alkoxy, branched chain alkoxy, halogen, nitrile of C3 ~ C10 of _{C1 ~ C10, CF 3, Si} (CH 3) 3 and Si (C ₆ H _{5) 3} An aryl group having 6 to 30 carbon atoms or a heteroaryl group having 5 to 60 carbon atoms which is substituted or unsubstituted with at least one substituent selected from
R7 and R8 are each independently selected from the group consisting of a hydrogen atom, C1-C10 straight chain alkyl, C3-C10 branched alkyl, C1-C10 cycloalkyl, C1-C10 linear alkoxy, C3- _{nitrile, CF 3, Si (CH 3} ) 3 or Si (C ₆ H _{5) 3,} or,
C 1 -C 10 straight chain alkoxy, halogen, nitrile, nitro, CF ₃ , Si (CH ₃ ) ₃ , C 1 -C 10 linear or branched alkyl, (C ₆ H ₅ ) ₃ , phenyl, naphthyl, phenanthrenyl, fluorenyl, tetrahydropyrrole, pyrrole, thienyl, thienyl, Thiophene, pyrazole, oxazolyl, triazole, pyridinyl, pyrimidinyl, triazinyl, imidazole, benzoxazole, benzothiazole, carbazole, dibenzofuran, dibenzothiophene, benzimidazole, Quinolinyl, indole, pyrenyl or

Lt; / RTI >
R7 and R8 are bonded to, a small wish chair, C1 ~ C10 straight chain alkyl, branched alkyl, halogen, nitrile of _{C3 ~ C10, CF 3, Si} (CH 3) 3, Si (C 6 H 5) 3, phenyl , A biphenyl and a naphthyl group, or a substituted or unsubstituted C1-C4 alkylene, biphenyl, naphthyl, phenanthrenyl, fluorenyl, benzoxazole, benzothiazole, Carbazole, dibenzofuran, dibenzothiophene, benzimidazole, quinoline, indole, pyrenyl,

,

,

,

,

or

Each of R9, R10, R11 and R12 is independently selected from the group consisting of a hydrogen atom, a C1 to C10 linear alkyl, a C3 to C10 branched alkyl, a C1 to C10 linear alkoxy, a C3 to C10 branch chain alkoxy, halogen, nitrile, acetyl alkylenyl, phenoxy, nitro, CF _3, phenoxy, Si (CH _{3) 3} or Si (C ₆ H _{5) 3,} or,
Small wish chair, C1 ~ C10 straight chain alkyl, branched alkyl, halogen, nitrile of _{C3 ~ C10, CF 3, Si} (CH 3) 3, Si (C 6 H 5) 3, phenyl, biphenyl and naphthyl groups A substituted or unsubstituted heterocyclic group selected from the group consisting of phenyl, naphthyl, phenanthrenyl, fluorenyl, pyridinyl, pyrimidinyl, triazinyl, imidazole, benzoxazole, benzothiazole, carbazole , Dibenzofuran, dibenzothiophene, benzimidazole, quinolinyl, indole, pyrenyl, or

Wherein R9 and R10 may combine to form a C1-C4 alkylene, and R10 and R11 may be combined to form a

,

,

,

or

And R11 and R12 may combine to form a C1-C4 alkylene. The method according to claim 1,
The aryl group having 6 to 30 carbon atoms or the heteroaryl group having 5 to 60 carbon atoms is preferably a phenyl, naphthyl, phenanthrenyl, fluorenyl, pyridinyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazinyl, imidazole, Wherein the electron transport compound is a triazole, benzoxazole, benzothiazole, carbazole, dibenzofuran, dibenzothiophene, benzimidazole, quinolinyl, indole or pyrenyl group. 3. The method of claim 2,
X is a carbon atom or a nitrogen atom;
R 1, R 2, R 3 and R 4 are each independently a hydrogen atom, a phenyl or biphenyl group;
R5 and R6 are the same, and a C1 ~ C10 straight chain alkyl, C3 ~ C10 straight chain of branched chain alkyl, C1 ~ C10 alkoxy, or a C3 ~ C10 branched alkoxy, halogen, nitrile, or CF ₃ each other,
C1 ~ C10 straight chain alkyl, C3 ~ C10 branched chain alkyl, straight chain alkoxy, branched chain alkoxy, halogen, nitrile of C3 ~ C10 ~ C10 of the C1, CF _3, phenyl, biphenyl, carbazole and

Naphthyl or fluorenyl group which is unsubstituted or substituted with one or more substituents selected from the group consisting of C1-C10 straight-chain alkyl, substituted or unsubstituted C3-C10 branched alkyl group, Unsubstituted phenyl, biphenyl, fluorenyl or pyridinyl group;
R7 and R8 are, each independently, a hydrogen atom, C1 ~ C10 straight chain alkyl, a C3 ~ C10 branched alkyl, C1 ~ C10 cycloalkyl, halogen, or nitrile, or CF _3;
C1 ~ C10 straight chain alkyl, unsubstituted or substituted with one or more substituents selected from the group consisting of C3 ~ C10 branched alkoxy, halogen, nitrile, nitro and CF _3, phenyl, tetrahydro-pyrrole, thiophenyl,

Lt; / RTI >
R7 and R8 are bonded to form a C1-C4 alkylene, a biphenyl, a naphthyl, a phenanthrenyl, a phenanthrenyl group, a phenanthrenyl group,

,

,

,

,

or

Wherein R9, R10, R11 and R12 are each independently selected from the group consisting of a hydrogen atom, C1 to C10 linear alkyl, C3 to C10 branched alkyl, C1 to C10 linear alkoxy, C3 to C10 branched alkoxy, halogen, nitrile, acetyl alkylenyl, _{nitro, CF 3, Si (CH 3} ) 3, phenyl, pyridinyl, phenoxy, quinolinyl or

Wherein R9 and R10 may combine to form a C1-C4 alkylene, and R10 and R11 may be combined to form a

,

,

,

or

And R11 and R12 may combine to form a C1-C4 alkylene. The method of claim 3,
Wherein the electron transport compound is any one of compounds 1-46, 48-61, 77-138, 142-152:

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